CN102066454A - Optically isomeric thin film material and optically isomeric thin film - Google Patents

Optically isomeric thin film material and optically isomeric thin film Download PDF

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CN102066454A
CN102066454A CN2009801225724A CN200980122572A CN102066454A CN 102066454 A CN102066454 A CN 102066454A CN 2009801225724 A CN2009801225724 A CN 2009801225724A CN 200980122572 A CN200980122572 A CN 200980122572A CN 102066454 A CN102066454 A CN 102066454A
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松山刚知
小林武史
椿幸树
渡边稔久
森吉弘
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Osaka Organic Chemical Industry Co Ltd
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Abstract

Disclosed is a liquid crystal polymer with minimal change in optical characteristics under high temperatures, a compound that contains the same, and a liquid crystal thin film polymerized therefrom. A polymer is polymerized by a reaction to add a polymer polymerized from a monomer represented by formula (I): (Wherein, R1 is H or methyl, A1, A2 are each a C1-4 alkylene or single bond, B1 is OH or COOH, X1 is a C1-18 alkylene, a C1-18 alkylene with -CO- on its phenoxy side, a C1-18 alkylene with a C1-6 alkylene bonded via -COO- on the opposite side, or a C1-18 alkylene with 1-10 -C2H40- bonded on the opposite side, and a, b are integers greater than 0, where a + b = 0 to 2) and an epoxy- or oxetane-inclusive cyclic monomer with an unsaturated bond-inclusive side chain, between B1 and the epoxy or oxetane.

Description

Light anisotropic thin mould material and light anisotropic films
Technical field
The present invention relates to light anisotropic thin mould material and light anisotropic films, more specifically relate to the polymerizable polymer that in side chain, has aromatic nucleus and two keys and comprise multi-functional liquid-crystal composition, the polymerizable liquid crystal film of this polymkeric substance and the light anisotropic films that this film is polymerized.
Background technology
In recent years, carried out the research of the liquid crystal liquid crystal property material of polymeric type of the two key positions of a large amount of employing polymerizabilitys by light or thermal response.Have optically anisotropic polymerizable liquid crystal material by polymerization, thereby the special optical characteristics before the polymerization is fixed by light or thermal initiation.Therefore, such polymerizable liquid crystal material has after the suitable orientation by make it under mesomorphic state that polymerization is solidified it under the state that keeps its orientation characteristic, thereby can obtain to keep the phase retardation film etc. of its optical characteristics to have optically anisotropic cured article.
In addition, also carried out a large amount of research (for example, patent documentation 1) for the technology that light anisotropic thin rete is formed in the liquid crystal cell.Compare with the prior art in the outside of the glass substrate that phase retardation film is pasted on liquid crystal,, can expect that then the aspects such as slimming, cost degradation at liquid crystal panel benefit if light anisotropic thin rete is located at the inside of liquid crystal cell.About this point, owing to the reason in the manufacturing process of liquid crystal panel, substrate that generally has been coated with liquid crystal material etc. is carrying out heat treated about 200 ℃ or under the higher temperature, so as the optical anisotropic material that is used for liquid crystal cell inside, even require to have the characteristic that optical anisotropy also can not change under the hot conditions of being exposed to.
In order to be easy to that the liquid crystal liquid crystal property macromolecule layer after the specific direction orientation is fixed, proposed to contain the polymer (for example, patent documentation 2) of crosslinkable groups.Yet there is the problem that aforesaid hot conditions optical characteristics of following time declines to a great extent that is exposed in the polymer that contains crosslinkable groups that is utilized.
Patent documentation 1: the Japanese Patent spy opens the 2000-221506 communique
Patent documentation 2: the Japanese Patent spy opens the 2005-257711 communique
The announcement of invention
Remain on the liquid crystal liquid crystal property film that optical characteristics also could not change or change few liquid-crystalline polymer and comprise the composition of this polymkeric substance and it is polymerized under the aforesaid hot conditions even the object of the present invention is to provide.
The inventor is provided at polymerizable polymer that has aromatic nucleus and two keys in the side chain and the multi-functional liquid-crystal composition that comprises this polymkeric substance, and the polymerizable liquid crystal film that adopts these liquid crystalline compositions also is provided.
The new polymerizable polymer that the inventor finds to have in side chain in the specified range of aromatic nucleus and two keys forms the optical anisotropic film with the character that meets above-mentioned purpose after polymerization, further study repeatedly and finished the present invention.That is, the invention provides following technical scheme.
1. polymerizable polymer, this polymkeric substance carries out addition reaction in containing of the hydroxyl of the described polymkeric substance (AP) that contains aromatic nucleus and/or carboxyl and described cyclic monomer between epoxy skeleton or the trimethylene oxide skeleton by the cyclic monomer that contains epoxy skeleton or trimethylene oxide skeleton that makes the polymkeric substance (AP) that contains aromatic nucleus and have a side chain (Q) that contains the ethene unsaturated link(age) and forms, and the described polymkeric substance (AP) that contains aromatic nucleus comprises with formula I by making:
Figure BPA00001277578400021
The expression (methyl) Acrylic Acid Monomer polymerizable monomer (PM) polymerization and form; In the formula, R 1Be hydrogen atom or methyl, A 1And A 2Independent respectively is the alkylidene group or the singly-bound of carbon number 1～4, B 1Be hydroxyl or carboxyl, X 1For
(i) alkylidene group of carbon number 1～18,
(ii) the phenoxy group side end of adjacency have the carbon number 1～18 of carbonyl alkylidene group,
(iii) the end of the opposition side of described phenoxy group side have Jie with the alkylidene group of the carbon number 1～18 of the alkylidene group of-COO-base bonded carbon number 1～6 or
(iv) the end at the opposition side of described phenoxy group side has 1～10-C of continuous bonded 2H 4The alkylidene group of the carbon number 1～18 of O-base,
A and b are 0 or positive integer and satisfy a+b=0～2.
2. as above-mentioned 1 polymerizable polymer, wherein, described polymerizable monomer (PM) also comprises with formula II:
Figure BPA00001277578400031
(methyl) Acrylic Acid Monomer of expression; In the formula, R 2Be hydrogen atom or methyl, A 3And A 4Respectively independent be carbon number 1～4 alkylidene group ,-COO-base or singly-bound, Z 1～Z 3Independent respectively is the alkyl of hydrogen atom, halogen atom, cyano group, carbon number 1～18 or the alkoxyl group of carbon number 1～4, X 2Be the alkylidene group of carbon number 1～18, c and d are 0 or positive integer and satisfy c+d=0～2.
3. as above-mentioned 1 or 2 polymerizable polymer, wherein, described cyclic monomer is with formula III:
Figure BPA00001277578400032
The aliphatic monomer that contains epoxy group(ing) of expression, with formula IV:
Figure BPA00001277578400033
The aliphatic monomer of the oxygen heterocyclic ring butane group of expression or with formula (V):
Figure BPA00001277578400034
The ester ring type monomer that contains epoxy group(ing) of expression; In the formula, R 3Be the alkyl of hydrogen atom or carbon number 1～4, R 4～R 6Be the alkyl of hydrogen atom or carbon number 1～4, R 7～R 15Alkyl for hydrogen atom or carbon number 1～4.
4. as each the polymerizable polymer in above-mentioned 1～3, wherein, the reactivity of the described polymkeric substance (AP) that contains aromatic nucleus and described cyclic monomer is at 5 moles more than the %.
5. multi-functional liquid-crystalline polymer composition, said composition comprise in above-mentioned 1～4 each polymerizable polymer and 1 molecule in have the multi-functional monomer of the ethene unsaturated link(age) more than 2.
6. as above-mentioned 5 multi-functional polymerizable polymer composition, wherein, multi-functional monomer is with formula VI:
Figure BPA00001277578400041
The multi-functional liquid crystal liquid crystal property monomer of expression; In the formula, R 16Be hydrogen atom or methyl, R 17Have for the alkylidene group of carbon number 1～18 or at the end of the opposition side of (methyl) acryloxy side of adjacency-the COO-base and-alkylidene group of the carbon number 1～18 of either party in the OCO-base, T 1For
Figure BPA00001277578400042
Z 4Be the alkyl of hydrogen atom, halogen atom, carbon number 1～18, Y 1For singly-bound or-COO-, Y 1' be singly-bound or-OCO-.
7. the liquid crystal panel polymer composition that comprises above-mentioned 5 or 6 multi-functional liquid-crystalline polymer composition.
8. above-mentioned 5 or 6 multi-functional liquid-crystalline polymer composition is coated the polymerizability film that substrate surface forms.
9. the optical anisotropic film that above-mentioned 5 or 6 multi-functional liquid-crystalline polymer composition is coated substrate surface and its curing is formed.
10. as above-mentioned 1 polymerizable polymer, wherein, described polymerizable monomer (PM) also comprises with formula II:
Figure BPA00001277578400043
(methyl) Acrylic Acid Monomer of expression,
With CH 2=CR 1-X 3The carboxylic monomer of-COOH (formula (C1)) expression and/or with CH 2=CR 1-X 4The carboxylic monomer of-COOH (formula (C2)) expression,
Described carboxylic monomeric total amount is below 15 weight % of the total amount of polymerizable monomer of representing with formula I (PM) and the polymerizable monomer represented with formula II; In the formula, R 2Be hydrogen atom or methyl, A 3And A 4Respectively independent be carbon number 1～4 alkylidene group ,-COO-base or singly-bound, Z 1～Z 3Independent respectively is the alkyl of hydrogen atom, halogen atom, cyano group, carbon number 1～18 or the alkoxyl group of carbon number 1～4, X 2Be the alkylidene group of carbon number 1～18, c and d are 0 or positive integer and satisfy c+d=0～2; In the formula (C1), R 1Be hydrogen or methyl, X 3For singly-bound or-COOR 2-, R 2Alkylidene group for carbon number 2～10; In the formula (C2), R 1Be hydrogen or methyl, X 4For-COOR 2OCOR 3-, R 2Be the alkylidene group of carbon number 2～10, R 3The aromatic alkylidene group that contains for the alkylidene group of carbon number 2～10 or carbon number 2～10.
11. as above-mentioned 10 polymerizable polymer, wherein, described cyclic monomer is with formula III:
Figure BPA00001277578400051
The aliphatic monomer that contains epoxy group(ing) of expression, with formula IV:
The aliphatic monomer of the oxygen heterocyclic ring butane group of expression or with formula (V):
Figure BPA00001277578400053
The ester ring type monomer that contains epoxy group(ing) of expression; In the formula, R 3Be the alkyl of hydrogen atom or carbon number 1～4, R 4～R 6Be the alkyl of hydrogen atom or carbon number 1～4, R 7～R 15Alkyl for hydrogen atom or carbon number 1～4.
12. as above-mentioned 10 or 11 polymerizable polymer, wherein, the reactivity of the described polymkeric substance (AP) that contains aromatic nucleus and described cyclic monomer is at 5 moles more than the %.
13. a multi-functional liquid-crystalline polymer composition, said composition comprise in above-mentioned 10～12 each polymerizable polymer and 1 molecule in have the multi-functional monomer of the ethene unsaturated link(age) more than 2.
14. as above-mentioned 13 multi-functional polymerizable polymer composition, wherein, multi-functional monomer is with formula VI:
Figure BPA00001277578400054
The multi-functional liquid crystal liquid crystal property monomer of expression; In the formula, R 16Be hydrogen atom or methyl, R 17Have for the alkylidene group of carbon number 1～18 or at the end of the opposition side of (methyl) acryloxy side of adjacency-the COO-base and-alkylidene group of the carbon number 1～18 of either party in the OCO-base, T 1For
Figure BPA00001277578400061
Z 4Be the alkyl of hydrogen atom, halogen atom, carbon number 1～18, Y 1For singly-bound or-COO-, Y 1' be singly-bound or-OCO-.
15. comprise the liquid crystal panel polymer composition of above-mentioned 13 or 14 multi-functional liquid-crystalline polymer composition.
16. above-mentioned 13 or 14 multi-functional liquid-crystalline polymer composition is coated the polymerizability film that substrate surface forms.
17. the optical anisotropic film that above-mentioned 13 or 14 multi-functional liquid-crystalline polymer composition is coated substrate surface and its curing is formed.
Use the film of said composition to have following favourable characteristics: to have good birefringent characteristic, even and be exposed to that birefringent characteristic can not change yet under the high temperature used when making liquid crystal panel.Therefore, if adopt composition of the present invention, then polymerizable liquid crystal film that not only can optical characteristics is good is located at the outside of liquid crystal cell, it can also be located in the liquid crystal cell, helps slimming, the cost degradation of liquid crystal panel.In addition, because not only at room temperature, at high temperature also can stably keep optical anisotropy, so also can be used as various electron devices and holographic material except that liquid crystal panel.
The best mode that carries out an invention
Polymerizable polymer of the present invention will comprise (methyl) Acrylic Acid Monomer (I) by making
Figure BPA00001277578400062
Polymerizable monomer (PM) polymerization and the polymkeric substance that contains aromatic nucleus (AP) that forms with the cyclic monomer reaction that contains epoxy skeleton or trimethylene oxide skeleton and form with the side chain (Q) that contains the ethene unsaturated link(age).
The A of formula I 1And A 2Independent respectively is the alkylidene group or the singly-bound of carbon number 1～4, better is singly-bound.B 1Being hydroxyl or carboxyl, better is carboxyl.X 1For the alkylidene group of (i) carbon number 1～18, (ii) have the alkylidene group of the carbon number 1～18 of carbonyl, (iii) have Jie with the alkylidene group of the carbon number 1～18 of the alkylidene group of-COO-base bonded carbon number 1～6 or (iv) have 1～10-C of continuous bonded at the end of the opposition side of phenoxy group side at the end of the opposition side of phenoxy group side at phenoxy group side end 2H 4The alkylidene group of the carbon number 1～18 of O-base.A and b are 0 or positive integer and satisfy a+b=0～2, from optical anisotropy and stable on heating viewpoint, better are 0 or positive integer and satisfy a+b=1～2.
The object lesson of (methyl) Acrylic Acid Monomer of representing with formula I is as follows.
Figure BPA00001277578400071
In the formula, n represents 1～18 integer, and R represents hydrogen atom or methyl, and G represents carboxyl.
Figure BPA00001277578400072
In the formula, n represents 1～18 integer, and R represents hydrogen atom or methyl, and G represents carboxyl.
Figure BPA00001277578400073
In the formula, m represents 1～5 integer, and n represents 1～18 integer, and R represents hydrogen atom or methyl, and G represents carboxyl.
Figure BPA00001277578400074
In the formula, n represents 1～18 integer, and R represents hydrogen atom or methyl, and G represents carboxyl.
Figure BPA00001277578400075
In the formula, n represents 1～18 integer, and R represents hydrogen atom or methyl, and G represents hydroxyl.
Figure BPA00001277578400076
In the formula, n represents 1～18 integer, and R represents hydrogen atom or methyl, and G represents carboxyl.
Among the present invention,, make above-mentioned polymkeric substance that contains aromatic nucleus (AP) and the cyclic monomer reaction that contains epoxy skeleton or trimethylene oxide skeleton with the side chain (Q) that contains the ethene unsaturated link(age) under hot conditions, giving the viewpoint of orientation characteristic.
As described example with cyclic monomer that contains epoxy skeleton or trimethylene oxide skeleton of the side chain (Q) that contains the ethene unsaturated link(age), the monomer of the oxygen heterocyclic ring butane group of can exemplify the aliphatic monomer that contains epoxy group(ing) represented with formula III, representing with formula IV, with the ester ring type monomer that contains epoxy group(ing) of formula (V) expression.
As the object lesson of the aliphatic monomer of representing with formula III that contains epoxy group(ing), but exemplified by methyl glycidyl acrylate, glycidyl acrylate, glycidyl itoconate, glycidyl allyl ether, methylallyl glycidyl ether etc.
Monomeric object lesson as the oxygen heterocyclic ring butane group of representing with formula IV, can exemplify 3-methyl trimethylene oxide-3-ylmethyl (methyl) acrylate, 3-ethyl trimethylene oxide-3-ylmethyl (methyl) acrylate, 3-n-propyl methyl trimethylene oxide-3-ylmethyl (methyl) acrylate, 3-sec.-propyl trimethylene oxide-3-ylmethyl (methyl) acrylate, 3-methyl trimethylene oxide-3-base ethyl (methyl) acrylate, 3-ethyl trimethylene oxide-3-base ethyl (methyl) acrylate, 3-n-propyl trimethylene oxide-3-base ethyl (methyl) acrylate, 3-sec.-propyl trimethylene oxide-3-base ethyl (methyl) acrylate, 2-methyl trimethylene oxide-3-ylmethyl (methyl) acrylate, 2,3-dimethyl trimethylene oxide-3-ylmethyl (methyl) acrylate, 2,4-dimethyl trimethylene oxide-3-ylmethyl (methyl) acrylate, 2,3,4-trimethylammonium trimethylene oxide-3-ylmethyl (methyl) acrylate, 3-ethyl-2-methyl trimethylene oxide-3-ylmethyl (methyl) acrylate, 3-ethyl-2,4-dimethyl trimethylene oxide-3-ylmethyl (methyl) acrylate etc.
As the monomeric object lesson of the ester ring type that contains epoxy group(ing) with formula (V) expression, can exemplify 3,4-epoxycyclohexyl methyl acrylate (Daisel chemical industry Co., Ltd (ダ イ セ Le chemical industry society) system, Daisel chemical industry Co., Ltd's system), 3 trade(brand)name: CYCLOMER-M-100), CYCLOMER-M-101 (trade(brand)name:, 4-epoxycyclohexyl methacrylic ester (Daisel chemical industry Co., Ltd's system, trade(brand)name: CYCLOMER-A-200), an epoxidized ethylene basic ring hexene, a Huan Yangization limonene etc.
Also have, the above-mentioned polymkeric substance (AP) that contains aromatic nucleus better is more than 5% with the reactivity with cyclic monomer that contains epoxy skeleton or trimethylene oxide skeleton of the side chain (Q) that contains the ethene unsaturated link(age), be more preferably more than 10%, further be more preferably more than 30%, and better be below 95%, be more preferably below 90%.Here " reactivity " is as giving a definition.
In addition, the acid number of polymerizable polymer better is below 160, is more preferably below 100.This is because if acid number is too high, then produces the problem of the transparency decline of orientation or film.
In addition, two key equivalents of polymerizable polymer better are in 200～3000 scope, are more preferably in 300～2000 scope.This is because if two key equivalent is too high, and then thermotolerance descends, if low excessively, then produces the problem that orientation descends.
When making polymerizable polymer of the present invention, can in above-mentioned polymerizable monomer (PM), add (methyl) Acrylic Acid Monomer that following formula II represents and make its polymerization.The interpolation of (methyl) Acrylic Acid Monomer of representing with formula II can make the softening temperature optimization of the polymerizable polymer of gained, so useful.
Formula II:
In the formula II, A 3And A 4Respectively independent be carbon number 1～4 alkylidene group ,-COO-base or singly-bound, better be-COO-base or singly-bound.Z 1～Z 3Independent respectively is the alkyl of hydrogen atom, halogen atom, cyano group, carbon number 1～18 or the alkoxyl group of carbon number 1～4, better is cyano group.X 2Be the alkylidene group of carbon number 1～18, c and d are 0 or positive integer and satisfy c+d=0～2, better are that c and d are 0 or positive integer and satisfy c+d=1～2.
The preferred example of (methyl) Acrylic Acid Monomer of representing with formula II is as follows.
Figure BPA00001277578400093
In the formula, n is 1～18 integer, and R is hydrogen atom or methyl, and G is a cyano group.
In the formula, n is 1～18 integer, and R is hydrogen atom or methyl, and G is a cyano group.
Figure BPA00001277578400101
In the formula, n is 1～18 integer, and R is independent respectively to be hydrogen atom or methyl.
Figure BPA00001277578400102
In the formula, n is 1～18 integer, and R is independent respectively to be hydrogen atom or methyl.
This polymerizable polymer of the present invention carries out addition reaction in containing of the hydroxyl of the described polymkeric substance (AP) that contains aromatic nucleus and/or carboxyl and described cyclic monomer between epoxy skeleton or the trimethylene oxide skeleton by the polymkeric substance that contains aromatic nucleus (AP) that makes the polymerizable monomer (PM) that will comprise (methyl) Acrylic Acid Monomer of representing with formula I and form and the cyclic monomer that contains epoxy skeleton or trimethylene oxide skeleton with the side chain (Q) that contains the ethene unsaturated link(age) and obtains.
Except (methyl) Acrylic Acid Monomer of representing with formula I, polymerizable monomer (PM) can comprise other monomers, but be not essential, such monomer is so long as have the compound of the ethene unsaturated link(age) of polymerizability and get final product, be not particularly limited in addition aspect, can not have liquid crystal liquid crystal property.
In the described polymkeric substance (AP) that contains aromatic nucleus, constitute its (methyl) Acrylic Acid Monomer of representing with formula I ratio with respect to this monomer with except that the monomeric total amount it in the scope of 0.1～100.0 weight %, better be in the scope of 5.0～95.0 weight %, be more preferably in the scope of 20.0～80.0 weight %.
As the monomer beyond (methyl) Acrylic Acid Monomer of representing divided by formula I, can exemplify for example (methyl) methyl acrylate, (methyl) tert-butyl acrylate, (methyl) stearyl acrylate base ester, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid ethoxy ethyl ester, (methyl) Hydroxyethyl Acrylate, (methyl) phenyl acrylate, N, (methyl) Acrylic Acid Monomers such as N-DMAA, vinylbenzene, alpha-methyl styrene, p styrene sulfonic acid, ethyl vinyl ether, the N-vinyl imidazole, vinyl-acetic ester, vinyl pyridine, the 2-vinyl naphthalene, vinylchlorid, vinyl fluoride, the N-vinylcarbazole, vinyl-amine, vinylphenol, vinyl monomers such as N-vinyl-2-Pyrrolidone, 4-allyl group-1, the 2-dimethoxy benzene, the 4-chavicol, allylic monomers such as 4-methoxyl group allyl benzene.
As above-mentioned other monomers, also can exemplify with CH 2=CR 1-X 3The carboxylic monomer of-COOH (formula (C1)) expression and/or with CH 2=CR 1-X 4The carboxylic monomer of-COOH (formula (C2)) expression; In the formula (C1), R 1Be hydrogen or methyl, X 3For singly-bound or-COOR 2-, R 2Alkylidene group for carbon number 2～10; In the formula (C2), R 1Be hydrogen or methyl, X 4For-COOR 2OCOR 3-, R 2Be the alkylidene group of carbon number 2～10, R 3The aromatic alkylidene group that contains for the alkylidene group of carbon number 2～10 or carbon number 2～10.But the carboxylic monomeric total amount of these formulas (C1) and formula (C2) is below 15 weight % of the total amount of the polymerizable monomer of the polymerizable monomer of formula I and formula II.This is that then molecular orientation is easy to generate confusion because if be higher than 15 weight parts, albefaction and optically anisotropic forfeiture when the polymkeric substance of coating gained takes place easily.
In addition, the polymkeric substance (AP) that contains aromatic nucleus is by making the monomer of formula I, the monomer polymerization of the monomer of the monomer of formula II and formula (C1) and/or formula (C2) and under the situation about forming, the monomeric usage quantity of formula I is made as M1, the monomeric usage quantity of formula II is made as M2, when the monomeric usage quantity of formula (C1) and/or formula (C2) is made as M3, the relatively good M1 of being of the monomeric amount of in the polymerization process these is 10～60 weight parts, M2 is that 90～40 weight parts and M3 are 1～15 weight part, and being more preferably M1 is 20～60 weight parts, M2 is that 80～40 weight parts and M3 are 2～12 weight parts.
As the carboxylic monomeric object lesson of formula (C1) or formula (C2), can exemplify (methyl) vinylformic acid, (methyl) acryloxy ethyl list phthalic ester, (methyl) acryloxy ethyl list tetrahydrophthalic acid ester, (methyl) acryloxy propyl group list tetrahydrophthalic acid ester, (methyl) acryloxy propyl group list tetrahydrophthalic acid ester, (methyl) acryloxy ethyl monosuccinic acid ester, ω-carboxyl-polycaprolactone list (methyl) acrylate, acrylic acid dimer, 4-(methyl) acryloxy ethyl benzoate etc.
With respect to the usage ratio of the cyclic monomer that contains epoxy skeleton or trimethylene oxide skeleton with the side chain (Q) that contains the ethene unsaturated link(age) of 1 mole of (methyl) Acrylic Acid Monomer of representing with formula I 0.01～3.0 mole, better be 0.1～2.1 mole, be more preferably 0.1～1.3 mole, further be more preferably in 0.2～1.3 mole the scope.
Polymerizable polymer of the present invention can suitably add the composition that comprises usually as in the Polymerizable compositions by light or thermal-initiated polymerization such as light trigger, addition reaction catalyst, tensio-active agent, solvent, provides with the form of polymerizable polymer composition.
The content of these solution compositions is not particularly limited, it better is gross weight with respect to the polymerizable polymer composition, the content of light trigger is in the scope of 0～30.0 weight %, the content of addition reaction catalyst is in the scope of 0～1.0 weight %, the content of tensio-active agent is in the scope of 0～10.0 weight %, and the content of organic solvent is in the scope of 0～90.0 weight %.
The cyclic monomer that contains epoxy skeleton or trimethylene oxide skeleton that makes the polymkeric substance (AP) that contains aromatic nucleus and have a side chain (Q) that contains the ethene unsaturated link(age) is in the described hydroxyl of polymkeric substance (AP) and/or the containing in the polymerizable polymer of the present invention that carries out addition reaction between epoxy skeleton or the trimethylene oxide skeleton and form of carboxyl and described cyclic monomer that contains aromatic nucleus, possible unreacted and residual polymkeric substance that contains aromatic nucleus (AP) and cyclic monomer better are whole for a small amount of with respect to polymerizable polymer, for example below the 0.5 weight %, to a certain degree remainingly also can realize purpose of the present invention even have, as long as in such scope, remaining quantity is not particularly limited.
The polymkeric substance (AP) that contains aromatic nucleus of the present invention can synthesize by making polymerizable monomer (PM) (independent monomeric mixture more than a kind or 2 kinds) polymerization.Polymerization can be carried out under solvent-free condition, also can be mixed in the solvent and carry out.The method of adding material and solvent etc. in the polymerization process is not particularly limited, begin polymerization after can in polymerization forward reaction container, dropping into all material in advance, also can be after a part that makes (methyl) Acrylic Acid Monomer or solvent etc. begins polymerization by drip or in batches method such as input append interimly.
In solution, under the polymeric situation, can adopt general organic solvent without particular limitation.Object lesson as solvent, can exemplify alcoholic solvents such as water or methyl alcohol, ethanol, propyl alcohol, butanols, Stearyl alcohol, ketones solvents such as acetone, methyl ethyl ketone, mibk, pimelinketone, cyclopentanone, esters solvent such as butylacetate, propylene glycol methyl ether acetate, ether solvent such as diethyl ether, diglyme, varsols such as hexane, hexanaphthene, methylcyclohexane, toluene, dimethylbenzene, nitrile solvents such as acetonitrile, amide solvents such as N-Methyl pyrrolidone, N,N-DIMETHYLACETAMIDE etc.
Can use polymerization starter in the polymerization of the above-mentioned polymkeric substance (AP) that contains aromatic nucleus.Polymerization starter can be usually used polymerization starter, as object lesson, can exemplify Diisopropyl azodicarboxylate (AIBN), diethyl-2,2 '-azo-bis-isobutyrate (V-601), 2,2 '-azo two (2, the 4-methyl pentane nitrile), azo class polymerization starter such as dimethyl azo dimethyl propylene acid esters, peroxide polymerization starters such as benzoyl peroxide, Potassium Persulphate, hydrogen peroxide, lauroyl peroxide, persulphate class polymerization starters such as Potassium Persulphate, ammonium persulphate etc.These polymerization starters can use any separately, also can more than 2 kinds and use.
Temperature during above-mentioned polymerization better is in 40～150 ℃ scope according to the kind of polymerizable monomer (PM), polymer solvent kind, initiator type etc. and different, is more preferably in 50～120 ℃ scope.
Polymerizable polymer of the present invention can carry out addition reaction between epoxy skeleton or the trimethylene oxide skeleton and obtains in the former hydroxyl and/or containing of the carboxyl and the latter by making the above-mentioned cyclic monomer that contains epoxy skeleton or trimethylene oxide skeleton that contains the polymkeric substance (AP) of aromatic nucleus and have a side chain (Q) that contains the ethene unsaturated link(age).The temperature of addition reaction is more preferably in 40～100 ℃ scope according to the kind of the kind of the kind of described cyclic monomer, reaction solvent, catalyzer and difference better is in 30～120 ℃ scope.
As the catalyzer in the above-mentioned addition reaction, can exemplify amino class catalyzer such as octylame, dibutylamine, monoethanolamine, trolamine, benzylamine, triethylamine, tetramethylammonium chloride, tetraethylammonium chloride, Variquat B 200,3-ethyl benzyl ammonium chloride, acetate Tetrylammonium, bromination four positive fourth ammoniums, iodate four positive fourth ammoniums, bromination triethyl hexadecyldimethyl benzyl ammonium, brominated diphenyl base iodine
Figure BPA00001277578400131
, quaternary ammonium salt such as bromination triphenylsulfonium, bromination three n-octyl sulfoniums, chlorinated triphenyl base sulfonium, tetraethyl-ammonium bromide, phosphor catalysts such as trimethyl-phosphine, triphenylphosphine, three (4-aminomethyl phenyl) phosphine, diphenylphosphino chloride etc.
From preventing viewpoint painted and the inhibition by product, the catalytic amount that uses in the above-mentioned addition reaction better is 0.0001～0.1 mole with respect to 1 mole of described cyclic monomer, is more preferably 0.003～0.05 mole.
Multi-functional liquid-crystalline polymer composition of the present invention is to comprise the multi-functional monomer combination that has the ethene unsaturated link(age) more than 2 in above-mentioned polymerizable polymer and 1 molecule, can uniform mixing obtains by both are stirred.Mixing so multi-functional monomer in polymerizable polymer is useful for the raising that is orientated stabilization and film forming stabilization.
As the multi-functional monomer that has the ethene unsaturated link(age) more than 2 in 1 molecule, can exemplify for example multifunctional (methyl) acrylate monomer, multifunctional (methyl) acrylamide monomer, polyfunctional vinyl monomer, multifunctional allyl monomer.
Object lesson as multifunctional (methyl) acrylate monomer, can exemplify ethylene glycol bisthioglycolate (methyl) acrylate, Diethylene Glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, ten TEG two (methyl) acrylate, dipropylene glycol two (methyl) acrylate, 1,3-butyleneglycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, tetramethylol methane four (methyl) acrylate, 1,4-butyleneglycol two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol six (methyl) acrylate etc.
Object lesson as multifunctional (methyl) acrylamide monomer can exemplify N, N '-methylene diacrylamine and by synthetic such as quadrol, phenylenediamine multifunctional (methyl) acrylamide etc.
As the monomeric object lesson of polyfunctional vinyl, can exemplify Vinylstyrene, ethylene glycol bisthioglycolate vinyl ether, hexanodioic acid divinyl ester, Succinic Acid divinyl ester etc.
As the object lesson of multifunctional allyl monomer, can exemplify Phthalic acid, diallyl ester, diallyl ether, propanedioic acid diallyl, to allyl styrene etc.
As multi-functional monomer, better be multifunctional (methyl) acrylate monomer, wherein good especially is the multi-functional liquid crystal liquid crystal property monomer of representing with formula VI, can exemplify for example following monomer.These multi-functional monomers can use any separately, also can more than 2 kinds and use.
Figure BPA00001277578400141
In the formula, n is 1～18 integer, and R is hydrogen atom or methyl.
Figure BPA00001277578400142
In the formula, n is 1～18 integer, and R is hydrogen atom or methyl, and Z is the alkyl of hydrogen atom, halogen atom or carbon number 1～8.
Figure BPA00001277578400143
In the formula, n is 1～18 integer, and R is hydrogen atom or methyl, and Z is the alkyl of hydrogen atom, halogen atom or carbon number 1～8.
Multi-functional liquid-crystalline polymer composition of the present invention can comprise known general Photoepolymerizationinitiater initiater in order to form uniform film by a spot of illumination.
Object lesson as Photoepolymerizationinitiater initiater; can exemplify IRGACURE 907 (Ciba company (チ バ ス ペ シ ヤ Le テ イ ケ ミ カ Le ズ society) system); IRGACURE 369 alpha-amino group ketone Photoepolymerizationinitiater initiaters such as (Ciba corporate systems); 4-phenoxy group Er Lvyixianben; 4-tertiary butyl Er Lvyixianben; the diethoxy phenyl methyl ketone; 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl third-1-ketone; the 1-hydroxycyclohexylphenylketone; 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-Ding-phenyl methyl ketone class Photoepolymerizationinitiater initiaters such as 1-ketone; bitter almond oil camphor; benzoin methyl ether; the bitter almond oil camphor ethyl ether; the bitter almond oil camphor isopropyl ether; bitter almond oil camphor class Photoepolymerizationinitiater initiaters such as benzil dimethyl ketal; benzophenone; benzoylbenzoic acid; the benzoylbenzoic acid methyl esters; 4-phenyl benzophenone; hydroxy benzophenone; propylene acidylate benzophenone; 4-benzoyl-4 '-Benzophenones Photoepolymerizationinitiater initiaters such as dimethyl diphenyl sulfide; the 2-clopenthixal ketone; 2-methyl thioxanthone; isopropyl thioxanthone; 2; thioxanthene ketone Photoepolymerizationinitiater initiaters such as 4-di-isopropyl thioxanthone; 2; 4; 6-three chloro-s-triazines; 2-phenyl-4; 6-two (trichloromethyl)-s-triazine; 2-(p-methoxyphenyl)-4; 6-two (trichloromethyl)-s-triazine; 2-(p-methylphenyl)-4; 6-two (trichloromethyl)-s-triazine; 2-piperonyl-4; 6-two (trichloromethyl)-s-triazine; 2; 4-two (trichloromethyl)-6-styryl-s-triazine; 2-(naphthoyl-1-yl)-4; 6-two (trichloromethyl)-s-triazine; 2-(4-methoxyl group-naphthoyl-1-yl)-4; 6-two (trichloromethyl)-s-triazine; 2; 4-trichloromethyl-(piperonyl)-6-triazine; 2; 4-trichloromethyl (4 '-methoxyl-styrene)-triazines Photoepolymerizationinitiater initiaters such as 6-triazine; the carbazoles Photoepolymerizationinitiater initiater; the imidazoles Photoepolymerizationinitiater initiater; and alpha-acyloxy ester; acylphosphine oxide; the aminomethyl phenyl glyoxylic ester; benzil; 9; the 10-phenanthrenequione; camphorquinone; EAQ; 4; 4 '-diethyl isophthaloyl benzene; 3; 3 '; 4; 4 '-four (t-butylperoxy carbonyl) benzophenone; 4,4 '-diethylamino benzophenone; Photoepolymerizationinitiater initiaters such as thioxanthone etc.Photoepolymerizationinitiater initiater can use any separately, also can more than 2 kinds and use.
Multi-functional liquid-crystalline polymer composition of the present invention can comprise general tensio-active agent in order to form uniform film.As tensio-active agent, can exemplify for example following tensio-active agent: anionic surfactants such as sodium lauryl sulphate, ammonium lauryl sulfate, dodecyltriethanolamine sulfate, polyoxyalkylene alkyl vitriol, alkyl ether phosphate, oleoyl sodium succinate, potassium myristate, coco-nut oil fatty acid potassium, sodium lauroyl sareosine; Nonionic surfactants such as polyethylene glycol monolaurate, stearic acid sorbitan ester, tetradecanoic acid glyceryl ester, glyceryl dioleate, sorbitan stearate, sorbitan oleic acid ester; Cationic surfactants such as chlorination stearyl trimethyl ammonium, chlorination docosyl trimethyl ammonium, chlorination stearyl dimethyl benzyl ammonium, cetyltrimethylammonium chloride; Alkyl betaines such as lauryl betaine, alkyl sultaine, AMONYL 380LC, alkyl dimethyl Padil trimethyl-glycine, alkyl imidazoline, amphotericses such as sodium lauroyl sareosine, cocounut oil acyl both sexes guanidine-acetic acid sodium; And BYK-361, BYK-306, BYK-307 (Bi Ke chemistry Japanese firm (PVC Star Network ケ ミ one ジ ヤ パ Application society) system), Fluorad FC430 (Sumitomo 3M Co., Ltd. (Sumitomo ス リ one エ system society) system), MEGAFAC F171, R08 (Dainippon Ink. ﹠ Chemicals Inc's (big Japanese イ Application キ chemical industry society) system) etc.These tensio-active agents can use any separately, also can more than 2 kinds and use.
The multi-functional liquid-crystalline polymer composition of the application of the invention can be made the film of the used for electronic device of good thermal stability.Its manufacture method is as follows, but is not limited to these methods.
When making film, for example with multi-functional liquid-crystalline polymer composition of the present invention directly or add solvent and coat after diluting on base material, for example film, remove and desolvate, form liquid crystal layer, perhaps further make its curing, getting final product liquid crystal layer is fixing by illumination.As the coating process of multi-functional liquid-crystalline polymer composition, can be any means known in this area, for example there are spin-coating method, rod to be coated with method, silk screen print method, spraying method etc.Form liquid crystal layer by removing behind the coating composition to desolvate as the layer of composition.Solvent is removed and can be adopted any means, proceed to resin layer with certain form immobilization till.Then, filming of drying operation makes its photopolymerization after further heat-treating.
The preferred example of solvent is toluene, glycerine, monoacetin, ethylene glycol, triethylene glycol, hexylene glycol, ethylene glycol monomethyl ether, glycol dimethyl ether, dibutyl ether, acetone, methyl ethyl ketone, ethanol, propyl alcohol, hexanaphthene, methylcyclohexane, tetrahydrofuran (THF), pimelinketone, normal hexane, ethyl acetate, butylacetate, N-Methyl pyrrolidone, N,N-DIMETHYLACETAMIDE etc.They can use any separately, also can more than 2 kinds and use.
As spendable base material, can exemplify for example glass baseplate such as alkali-containing glass, non-alkali glass, resin base materials such as polyimide, polymeric amide, acrylic resin, polyvinyl alcohol, triacetyl cellulose, polyethylene terephthalate, polyethylene, polycarbonate, polystyrene, voltalef, metal bases such as iron, aluminium, copper etc.; It better is glass substrate.The substrate of change of properties when better being the high temperature that is heated to more than 200 ℃, base material also can not take place.
The thermal treatment of filming better is to carry out with the condition that liquid crystal can obtain the homogeneous orientation.As heat treating method, the orientation of being heated to filming method etc. of temperature postcooling of homogeneous that becomes is for example arranged.Thermal treatment better is in 20 ℃～120 ℃ temperature range, is more preferably in 50 ℃～100 ℃ temperature range.From the viewpoint of production efficiency, thermal treatment better is in the scope in treatment time of 10 seconds～3 hours, is more preferably in the scope in treatment time of 30 seconds～20 minutes.
As the used light source of illumination, can adopt xenon lamp, high voltage mercury lamp, excimer laser, sodium vapor lamp, halogen lamp, backlight, electron rays irradiation etc.
Light wavelength is unqualified, better is 150～800nm, is more preferably 180～600nm.
Light quantity is unqualified, better is 20～5000mJ/cm 2, be more preferably 100～1500mJ/cm 2
The thickness of film of the present invention better is in the scope of 0.1～20.0 μ m, is more preferably in the scope of 1.0～5.0 μ m.
The film of making by method of the present invention can be used as the image quality that blooming etc. performs well in liquid crystal panel and improves.Composition particularly of the present invention not only can be formed at whole of the substrate of display panels, can also form film independently at the privileged site (pixel) of substrate.
Embodiment
1. polymkeric substance (AP) synthetic that contains aromatic nucleus
(embodiment 1) contains polymkeric substance (X-1) (monomer ratio, the I-a1: II-a1=40: 60) synthetic of aromatic nucleus
With 4.0g (0.011mol) with formula (I-a1):
Figure BPA00001277578400171
The Acrylic Acid Monomer, 6.0g (0.017mol) of expression with formula (II-a1):
Figure BPA00001277578400172
The Acrylic Acid Monomer, 30.0g pimelinketone of expression mix and solution under stream of nitrogen gas, mixed 1 hour; (in the I-a1), n is 6 to formula, G 1Be carboxyl; (in the II-a1), n is 6 to formula, G 2Be cyano group.Then, mixing solutions is heated to after the liquid temperature reaches 75 ℃, drops into 0.10g polymerization starter Diisopropyl azodicarboxylate (AIBN), in 75～85 ℃ temperature range, carry out 8 hours polyreaction.Consequently, obtain the polymer composition that 40.1g contains aromatic nucleus, wherein comprise the polymkeric substance (X-1) that 10.0g contains aromatic nucleus.
The mensuration of＜weight-average molecular weight (MW) 〉
Use gel filtration chromatography (GPC) to measure the weight-average molecular weight (MW) of the polymkeric substance (X-1) that contains aromatic nucleus.The weight-average molecular weight (MW) of the polymkeric substance that contains aromatic nucleus of gained is 18000.
The mensuration of＜acid number 〉
Measuring method is as follows.That is, get about 60ml ethanol, phenolphthalein as indicator, is neutralized with the 0.1mol/l aqueous sodium hydroxide solution to the 100ml Erlenmeyer flask.The about 1.5g polymer composition of precision weighing is dissolved in above-mentioned solution equably, stirs the back and carries out titration with the 0.1mol/l aqueous sodium hydroxide solution, and the time point that blush was not disappeared in about 30 seconds is as titration end point.
Calculate acid number according to following formula.
Acid number=(0.1 * f * A * 56.1/B)/(C/100)
A: titer (ml)
F: the coefficient of aqueous sodium hydroxide solution
B: polymer composition amount (g)
C: polymer concentration (%)
(amount of polymers/polymer composition amount * 100)
The above-mentioned acid number that contains the polymkeric substance (X-1) of aromatic nucleus is 61mgKOH/g.
(embodiment 2) contain polymkeric substance (X-2) (monomer ratio, the I-a1: II-a1=50: 50) synthetic of aromatic nucleus
Except will (usage quantity of (methyl) Acrylic Acid Monomer of the expression of I-a) changes 5.0g (0.014mol) into, (usage quantity of (methyl) Acrylic Acid Monomer of expression of II-a) changes into the 5.0g (0.014mol), implements similarly to Example 1 with formula with formula.
The weight-average molecular weight (MW) of the polymkeric substance that contains aromatic nucleus (X-2) of gained is 14000, and acid number is 77mgKOH/g.
(embodiment 3) contain polymkeric substance (X-3) (monomer ratio, the I-a1: II-a1=100: 0) synthetic of aromatic nucleus
Except will (usage quantity of (methyl) Acrylic Acid Monomer of the expression of I-a) changes 10.0g (0.027mol) into, (II-a) usage quantity of (methyl) Acrylic Acid Monomer of expression changes into 0, implements similarly to Example 1 with formula with formula.
The weight-average molecular weight (MW) of the polymkeric substance that contains aromatic nucleus (X-3) of gained is 18000, and acid number is 152mgKOH/g.
(embodiment 4) contain polymkeric substance (X-4) (monomer ratio, the I-f1: II-a1=40: 60) synthetic of aromatic nucleus
Except use 4.0g (0.014mol) with (I-f1):
The Acrylic Acid Monomer of expression replaces (beyond the Acrylic Acid Monomer of the expression of I-a1), to implement similarly to Example 1; (in the I-f1), n is 6 to formula, G 3Be carboxyl.
The weight-average molecular weight (MW) of the polymkeric substance that contains aromatic nucleus (X-4) of gained is 18000, and acid number is 77mgKOH/g.
(embodiment 5) contain polymkeric substance (X-5) (monomer ratio, the I-f1: II-a1=20: 80) synthetic of aromatic nucleus
Except will (usage quantity of the Acrylic Acid Monomer of the expression of I-f1) changes 2.0g (0.007mol) into, (usage quantity of (methyl) Acrylic Acid Monomer of expression of II-a1) changes into the 8.0g (0.022mol), implements similarly to Example 4 with formula with formula.
The weight-average molecular weight (MW) of the polymkeric substance that contains aromatic nucleus (X-5) of gained is 16000, and acid number is 38mgKOH/g.
(comparative example 1) contains polymkeric substance (X-6) (monomer ratio, the I-a1: II-a1=0: 100) synthetic of aromatic nucleus
Except will (usage quantity of (methyl) Acrylic Acid Monomer of the expression of I-a1) changes 0 into, (usage quantity of (methyl) Acrylic Acid Monomer of expression of II-a1) changes into the 10.0g (0.028mol), implements similarly to Example 1 with formula with formula.
The weight-average molecular weight (MW) of the polymkeric substance that contains aromatic nucleus (X-6) of gained is 20000, and acid number is 0mgKOH/g.
2. synthetic (with the addition reaction of cyclic monomer) of polymerizable polymer
(embodiment 6) polymerizable polymers (Y-1) (monomer ratio=40: 60 situation) synthetic
Synthetic among the 40.1g embodiment 1 contained the polymer composition (monomer ratio=40: 60) (polymkeric substance (X-1) 10.0g that contains aromatic nucleus) of aromatic nucleus while stir and heat, under 60 ℃ liquid temperature, drop into 1.54g (0.011mol, MW142) glycidyl methacrylate (GMA), 0.006g stopper hydroquinone monomethyl ether (MEHQ) and 0.019g (0.000143mol) esterifying catalyst dimethyl benzyl amine, continuing heating then, is 95～105 ℃ scope internal reaction in temperature of reaction.The acid number reactivity reaches 90.0% when above, and reacting liquid temperature is cooled to below 30 ℃, finishes reaction.Then, drop into the 4.43g pimelinketone, obtain 46.16g polymerizable polymer composition (comprising 11.54g polymerizable polymer (Y-1)) while stir.The weight-average molecular weight of the polymerizable polymer of gained (MW) is 24000, and acid number is 4mgKOH/g.
The acid number reactivity is calculated according to following formula.
Figure BPA00001277578400201
Consequently, the acid number reactivity of resultant is 93%.
The normal mensuration of＜two keys 〉
Two key equivalents of above-mentioned polymerizable polymer (Y-1) (every 1mol ethene unsaturated group corresponding polymers weight) are calculated according to following formula.
Figure BPA00001277578400202
Consequently, two key equivalents are 1134.
(embodiment 7) polymerizable polymers (Y-2) (monomer ratio=50: 50 situation) synthetic
Synthetic among the 40.1g embodiment 2 contained the polymkeric substance (monomer ratio=50: 50) (polymkeric substance (X-2) 10.0g that contains aromatic nucleus) of aromatic nucleus while stir and heat, under 60 ℃ liquid temperature, drop into 1.93g (0.014mol) glycidyl methacrylate (GMA), 0.006g stopper hydroquinone monomethyl ether and 0.024g (0.000181mol) esterifying catalyst dimethyl benzyl amine, continuing heating then, is 95～105 ℃ scope internal reaction in temperature of reaction.The acid number reactivity reaches 90.0% when above, and reacting liquid temperature is cooled to below 30 ℃, finishes reaction.Then, drop into the 5.69g pimelinketone, obtain 47.72g polymerizable polymer composition (comprising 11.93g polymerizable polymer (Y-2)) while stir.The weight-average molecular weight of the polymerizable polymer of gained (MW) is 23000, and two key equivalents are 938, and acid number is 6mgKOH/g.In addition, the acid number reactivity is 91%.
(embodiment 8) polymerizable polymers (Y-3) (monomer ratio=100: 0 situation) synthetic
The above synthetic of 40.1g contained the polymkeric substance (monomer ratio=100: 0) (polymkeric substance (X-3) 10.0g that contains aromatic nucleus) of aromatic nucleus while stir and heat, under 60 ℃ liquid temperature, drop into 3.86g (0.028mol) glycidyl methacrylate (GMA), 0.006g stopper hydroquinone monomethyl ether and 0.049g (0.000368mol) esterifying catalyst dimethyl benzyl amine, continuing heating then, is 95～105 ℃ scope internal reaction in temperature of reaction.The acid number reactivity reaches 90.0% when above, and reacting liquid temperature is cooled to below 30 ℃, finishes reaction.Then, drop into the 11.48g pimelinketone, obtain 55.44g polymerizable polymer composition (comprising 13.86g polymerizable polymer (Y-3)) while stir.The weight-average molecular weight of the polymerizable polymer of gained (MW) is 25000, and two key equivalents are 504, and acid number is 2mgKOH/g.In addition, the acid number reactivity is 98%.
(embodiment 9) polymerizable polymers (Y-4) (monomer ratio=40: 60 situation) synthetic
The above synthetic of 40.1g contained the polymkeric substance (monomer ratio=40: 60) (polymkeric substance (X-4) 10.0g that contains aromatic nucleus) of aromatic nucleus while stir and heat, under 60 ℃ liquid temperature, drop into 1.93g (0.014mol) glycidyl methacrylate (GMA), 0.006g stopper hydroquinone monomethyl ether and 0.024g (0.000181mol) esterifying catalyst dimethyl benzyl amine, continuing heating then, is 95～105 ℃ scope internal reaction in temperature of reaction.The acid number reactivity reaches 90.0% when above, and reacting liquid temperature is cooled to below 30 ℃, finishes reaction.Then, drop into the 5.69g pimelinketone, obtain 47.72g polymerizable polymer composition (comprising the 11.93g polymerizable polymer) while stir.The weight-average molecular weight (MW) of the polymerizable polymer of gained (Y-4) is 24000, and two key equivalents are 893, and acid number is 3mgKOH/g.In addition, the acid number reactivity is 95%.
(embodiment 10) polymerizable polymers (Y-5) (monomer ratio=20: 80 situation) synthetic
The above synthetic of 40.1g contained the polymkeric substance (monomer ratio=20: 80) (polymkeric substance (X-5) 10.0g that contains aromatic nucleus) of aromatic nucleus while stir and heat, under 60 ℃ liquid temperature, drop into 0.97g (0.007mol) glycidyl methacrylate (GMA), 0.006g stopper hydroquinone monomethyl ether and 0.0126g (0.000095mol) esterifying catalyst dimethyl benzyl amine, continuing heating then, is 95～105 ℃ scope internal reaction in temperature of reaction.The acid number reactivity reaches 90.0% when above, and reacting liquid temperature is cooled to below 30 ℃, finishes reaction.Then, drop into the 2.81g pimelinketone, obtain 43.88g polymerizable polymer composition (comprising 10.97g polymerizable polymer (Y-5)) while stir.The weight-average molecular weight of the polymerizable polymer of gained (MW) is 18000, and two key equivalents are 1710, and acid number is 3mgKOH/g.In addition, the acid number reactivity is 92%.
3. multi-functional liquid-crystalline polymer composition is synthetic
Synthesizing of (embodiment 11) multi-functional liquid-crystalline polymer compositions (Z-1)
With input have 46.16g polymerizable polymer composition (comprising 11.54g polymerizable polymer (Y-1)), 17.31g with following formula (VI-a):
Figure BPA00001277578400211
The solution stirring of the multi-functional liquid crystal liquid crystal property monomer (weight with respect to polymerizable polymer (Y-1) is 1.5 times) of expression, 1.44g Photoepolymerizationinitiater initiater IRGACURE 907,86.54g pimelinketone was mixed 1 hour, obtained the multi-functional liquid-crystalline polymer composition of 151.45g; (in the VI-a), n is 6 to formula.About the contained solids component of composition of the multi-functional liquid-crystalline polymer (Z-1) of gained, two key equivalents are 468, and acid number is 2mgKOH/g.
Synthesizing of (embodiment 12) multi-functional liquid-crystalline polymer compositions (Z-2)
Except the polymerizable polymer composition (comprising 11.93g polymerizable polymer (Y-2)) that the polymerizable polymer composition is changed into 47.72g embodiment 7, (the multi-functional liquid crystal liquid crystal property monomer of VI-a) is (in the formula with following formula, n is 6) change 17.90g (weight with respect to polymerizable polymer (Y-2) is 1.5 times) in addition, implementation and operation similarly to Example 11.About the contained solids component of composition of the multi-functional liquid-crystalline polymer (Z-2) of gained, two key equivalents are 452, and acid number is 2mgKOH/g.
Synthesizing of (embodiment 13) multi-functional liquid-crystalline polymer compositions (Z-3)
Except the polymerizable polymer composition (comprising 13.86g polymerizable polymer (Y-3)) that the polymerizable polymer composition is changed into 55.44g embodiment 8, (the multi-functional liquid crystal liquid crystal property monomer of VI-a) is (in the formula with above-mentioned, n is 6) change 20.79g (weight with respect to polymerizable polymer (Y-3) is 1.5 times) in addition, implementation and operation similarly to Example 11.About the contained solids component of composition of the multi-functional liquid-crystalline polymer (Z-3) of gained, two key equivalents are 388, and acid number is 1mgKOH/g.
Synthesizing of (embodiment 14) multi-functional liquid-crystalline polymer compositions (Z-4)
Input is had 46.16g polymerizable polymer composition (comprising 11.54g polymerizable polymer (Y-1)), 17.31g, and (the multi-functional liquid crystal liquid crystal property monomer of the expression of VI-a) is (in the formula with following formula, n is 6), the solution stirring of 1.44g Photoepolymerizationinitiater initiater IRGACURE 907,86.54g pimelinketone, 0.029g BYK-323 (tensio-active agent) mixed 1 hour, obtained the multi-functional liquid-crystalline polymer composition of 151.48g.About the contained solids component of composition of the multi-functional liquid-crystalline polymer (Z-4) of gained, two key equivalents are 468, and acid number is 2mgKOH/g.
Synthesizing of (embodiment 15) multi-functional liquid-crystalline polymer compositions (Z-5)
Except the polymerizable polymer composition (comprising 11.93g polymerizable polymer (Y-4)) that the polymerizable polymer composition is changed into 47.72g embodiment 9, (the multi-functional liquid crystal liquid crystal property monomer of VI-a) changes 17.90g (weight with respect to polymerizable polymer (Y-4) is 1.5 times) in addition, similarly to Example 14 implementation and operation with following formula.About the contained solids component of composition of the multi-functional liquid-crystalline polymer (Z-5) of gained, two key equivalents are 448, and acid number is 1mgKOH/g.
Synthesizing of (embodiment 16) multi-functional liquid-crystalline polymer compositions (Z-6)
Except the polymerizable polymer composition (comprising 10.97g polymerizable polymer (Y-5)) that the polymerizable polymer composition is changed into 43.88g embodiment 10, (the multi-functional liquid crystal liquid crystal property monomer of VI-a) changes 16.46g (weight with respect to polymerizable polymer (Y-5) is 1.5 times) in addition, similarly to Example 14 implementation and operation with following formula.About the contained solids component of composition of the multi-functional liquid-crystalline polymer (Z-6) of gained, two key equivalents are 495, and acid number is 1mgKOH/g.
Synthesizing of (embodiment 17) multi-functional liquid-crystalline polymer compositions (Z-7)
Except the polymerizable polymer composition (comprising 13.86g polymerizable polymer (Y-3)) that the polymerizable polymer composition is changed into 55.44g embodiment 8, (the multi-functional liquid crystal liquid crystal property monomer of VI-a) changes 20.79g (weight with respect to polymerizable polymer (Y-3) is 1.5 times) in addition, similarly to Example 14 implementation and operation with following formula.About the contained solids component of composition of the multi-functional liquid-crystalline polymer (Z-7) of gained, two key equivalents are 388, and acid number is 1mgKOH/g.
Synthesizing of (comparative example 2) multi-functional liquid-crystalline polymer composition (Z-9)
Except the polymer composition that contains aromatic nucleus (monomer ratio=40: 60) (polymkeric substance (X-1) 10.0g that contains aromatic nucleus) that the polymerizable polymer composition is changed into 40.1g embodiment 1, implementation and operation similarly to Example 11.About the contained solids component of composition of the polymkeric substance (Z-9) of gained, two key equivalents are 560, and acid number is 24mgKOH/g.
Synthesizing of (comparative example 3) multi-functional liquid-crystalline polymer composition (Z-10)
Except the polymer composition that contains aromatic nucleus (monomer ratio=0: 100) (polymkeric substance (X-6) 10.0g that contains aromatic nucleus) that the polymerizable polymer composition is changed into 40.1g comparative example 1, implementation and operation similarly to Example 11.About the contained solids component of composition of the polymkeric substance (Z-10) of gained, two key equivalents are 560, and acid number is 0mgKOH/g.
The acid number of composition in the polymkeric substance manufacturing of the foregoing description and comparative example and ratio, polymkeric substance, two key equivalent, weight-average molecular weight gather and are shown in following table 1～table 3.
Table 1.
Figure BPA00001277578400241
Table 2.
Figure BPA00001277578400242
Table 3.
Figure BPA00001277578400251
4. for the performance evaluation of each multi-functional liquid-crystalline polymer composition
For each multi-functional liquid-crystalline polymer composition of making in the various embodiments described above and the comparative example, according to following step film forming, the delay (Re/d) of direction in the face of the delay (Rth/d) of the thickness direction of the coating of each film, the transparency, unit thickness, unit thickness is estimated by following method.
＜film 〉
Handle film for (1) 90 ℃:
The multi-functional liquid-crystalline polymer composition of about 2ml is cast in substrate (glass and polyimide, 10 * 10cm 2) on, make film by spin coating after, make its drying (90 ℃/10 minutes) and make the alignment films of thick 2 μ m, be cooled to 30 ℃.
Handle film for (2) 230 ℃:
After the alignment films of as above making is cooled to 30 ℃, irradiation exposure 900mJ/cm 2UV-light and solidify, made film is carried out pyroprocessing (230 ℃/1～3 hour) after, be cooled to 30 ℃.
The evaluation of the transparency of＜coating and film 〉
For the film of as above making, by visual inspection based on following standard evaluation coating and the transparency and record.
Coating:
A: film uniform surface and good
B: observe a spot of inequality and pit (crater) etc.
C: observe a large amount of inequalities and pit etc.
The transparency of film:
Estimate for the film of as above making.
Zero: transparent
*: albefaction
The evaluation of＜optical characteristics 〉
For the film that as above obtains, measure by polarization analysis apparatus OPTIPRO (Xintai City Co., Ltd. of section (シ Application テ Star Network (strain)) system) with following condition, try to achieve Rth/d and Re/d.
Measure wavelength X: 550[nm]
The thickness d of film: 2[μ m]
＜evaluation result 〉
The result of above-mentioned evaluation gathers and is shown in following table 4～table 8.It is as shown in the table, though as can be known the multi-functional liquid-crystalline polymer composition of embodiment can provide have good birefringent characteristic, coating, the film transparency and expose the film that birefringent characteristic at high temperature also can not change.
Handle film for 90 ℃ on table 4. glass substrate
Figure BPA00001277578400261
Handle film for 90 ℃ on table 5. polyimide substrate
Figure BPA00001277578400262
230 ℃ of processing on table 6. glass substrate
Handle film for 230 ℃ on table 7. polyimide substrate
Figure BPA00001277578400272
230 ℃ of processing of table 8. polyimide substrate
Figure BPA00001277578400273
5. contain aromatic nucleus polymkeric substance (AP) synthetic-2
(embodiment 18) contain polymkeric substance (W-1) (monomer ratio, the I-a1: II-a1: methacrylic acid=40: 50: 10) synthetic of aromatic nucleus
With 4.0g (0.011mol) with formula (I-a1):
Figure BPA00001277578400281
The Acrylic Acid Monomer, 5.0g (0.017mol) of expression with formula (II-a1):
The Acrylic Acid Monomer, 1.0g methacrylic acid, 30.0g pimelinketone of expression mix and solution under stream of nitrogen gas, mixed 1 hour; (in the I-a1), n is 6 to formula, G 1Be carboxyl; (in the II-a1), n is 6 to formula, G 2Be cyano group.Then, mixing solutions is heated to after the liquid temperature reaches 75 ℃, drops into 0.1g polymerization starter Diisopropyl azodicarboxylate (AIBN), in 75～85 ℃ temperature range, carry out 8 hours polyreaction.Consequently, obtain the 40.1g polymer composition, wherein comprise the polymkeric substance (W-1) that 10.0g contains aromatic nucleus.
The mensuration of＜weight-average molecular weight (MW) 〉
Use gel filtration chromatography (GPC) to measure the weight-average molecular weight (MW) of the polymkeric substance (W-1) that contains aromatic nucleus.The weight-average molecular weight (MW) of the polymkeric substance that contains aromatic nucleus of gained is 18000.
The mensuration of＜acid number 〉
Measuring method is as follows.That is, get about 60ml ethanol, phenolphthalein as indicator, is neutralized with the 0.1mol/l aqueous sodium hydroxide solution to the 100ml Erlenmeyer flask.The about 1.5g polymer composition of precision weighing is dissolved in above-mentioned solution equably, stirs the back and carries out titration with the 0.1mol/l aqueous sodium hydroxide solution, and the time point that blush was not disappeared in about 30 seconds is as titration end point.
Calculate acid number according to following formula.
Acid number=(0.1 * f * A * 56.1/B)/(C/100)
A: titer (ml)
F: the coefficient of aqueous sodium hydroxide solution
B: polymer composition amount (g)
C: polymer concentration (%)
(amount of polymers/polymer composition amount * 100)
The above-mentioned acid number that contains the polymkeric substance (W-1) of aromatic nucleus is 34mgKOH/g.
(embodiment 19) contain polymkeric substance (W-2) (monomer ratio, the I-a1: II-a1: vinylformic acid=20: 70: 10) synthetic of aromatic nucleus
Except will (usage quantity of (methyl) Acrylic Acid Monomer of the expression of I-a) changes 2.0g (0.005mol) into, (usage quantity of (methyl) Acrylic Acid Monomer of expression of II-a) changes 7.0g (0.023mol) into and uses 1.0g vinylformic acid to replace implementing similarly to Example 18 the methacrylic acid with formula with formula.
The weight-average molecular weight (MW) of the polymkeric substance that contains aromatic nucleus (W-2) of gained is 14000, and acid number is 27mgKOH/g.
(embodiment 20) contain polymkeric substance (W-3) (monomer ratio, the I-a1: II-a1: ARONIX M-5300=30: 57: 13) synthetic of aromatic nucleus
Except will (usage quantity of (methyl) Acrylic Acid Monomer of the expression of I-a) changes 3.0g (0.008mol) into, (II-a) usage quantity of (methyl) Acrylic Acid Monomer of expression changes 5.7g (0.019mol) into and uses ARONIX M-5300 (ω-carboxyl-polycaprolactone (n ≈ 2) mono acrylic ester: CH with formula with formula 2=CHCOO-(C 5H 10COO) n-H, the (East Asia of Toagosei Co., Ltd synthesizes (strain)) system) replace implementing similarly to Example 1 beyond the methacrylic acid.
The weight-average molecular weight (MW) of the polymkeric substance of gained (W-3) is 14000, and acid number is 18mgKOH/g.
(comparative example 4) contains polymkeric substance (W-4) (monomer ratio, the I-a1: II-a1=40: 60) synthetic of aromatic nucleus
Except will (usage quantity of (methyl) Acrylic Acid Monomer of the expression of I-a) changes 4.0g (0.005mol) into, (usage quantity of (methyl) Acrylic Acid Monomer of expression of II-a) changes into the 6.0g (0.023mol), implements similarly to Example 1 with formula with formula.
The weight-average molecular weight (MW) of the polymkeric substance of gained (W-2) is 22000, and acid number is 15mgKOH/g.
(comparative example 5) contains polymkeric substance (W-5) (monomer ratio, the I-a1: II-a1: vinylformic acid=20: 60: 20) synthetic of aromatic nucleus
Except will (usage quantity of (methyl) Acrylic Acid Monomer of the expression of I-a) changes 2.0g (0.005mol) into, (usage quantity of (methyl) Acrylic Acid Monomer of expression of II-a) changes 6.0g (0.023mol) into and uses the 2.0g vinylformic acid, implements similarly to Example 1 with formula with formula.
The weight-average molecular weight (MW) of the polymkeric substance of gained (W-2) is 14000, and acid number is 46mgKOH/g.
6. synthetic (with the addition reaction of cyclic monomer)-2 of polymerizable polymer
(embodiment 21) polymerizable polymers (XX-1) (monomer ratio, I-a1: II-a1: the situation of methacrylic acid=40: 50: 10) synthetic
(polymkeric substance (W-1) 10.0g that contains aromatic nucleus) heats while stirring with synthetic polymer composition among the 40.1g embodiment 18, under 60 ℃ liquid temperature, drop into 1.5g (0.011mol, MW142) glycidyl methacrylate (GMA), 0.006g stopper hydroquinone monomethyl ether (MEHQ) and 0.02g (0.000143mol) esterifying catalyst dimethyl benzyl amine, continuing heating then, is 95～105 ℃ scope internal reaction in temperature of reaction.With following formula:
Figure BPA00001277578400301
The acid number reactivity of definition reaches 90.0% when above, and reacting liquid temperature is cooled to below 30 ℃, finishes to react.Then, drop into the 4.4g pimelinketone, obtain 46.0g polymerizable polymer composition (comprising 11.4g polymerizable polymer (XX-1)) while stir.The weight-average molecular weight of the polymerizable polymer of gained (MW) is 24000, and acid number is 18mgKOH/g.
The normal mensuration of＜two keys 〉
Two key equivalents of above-mentioned polymerizable polymer (XX-1) (every 1mol ethene unsaturated group corresponding polymers weight) are calculated according to following formula.
Figure BPA00001277578400302
Consequently, two key equivalents are 1150.
(embodiment 22) polymerizable polymers (XX-2) (monomer ratio, I-a1: II-a1: the situation of vinylformic acid=20: 70: 10) synthetic
The polymkeric substance (polymkeric substance (W-2) 10.0g that contains aromatic nucleus) that synthetic among the 40.1g embodiment 19 is contained aromatic nucleus heats while stirring, under 60 ℃ liquid temperature, drop into 1.6g (0.008mol, MW:200) the acrylate-based glycidyl ether of 4-hydroxybutyl (4HBAGE), 0.006g stopper hydroquinone monomethyl ether and 0.002g (0.000163mol) esterifying catalyst dimethyl benzyl amine, continuing heating then, is 95～105 ℃ scope internal reaction in temperature of reaction.The acid number reactivity reaches 90.0% when above, and reacting liquid temperature is cooled to below 30 ℃, finishes reaction.Then, drop into the 3.7g pimelinketone, obtain 45.4g polymerizable polymer composition (comprising 11.4g polymerizable polymer (XX-2)) while stir.The weight-average molecular weight of the polymerizable polymer of gained (MW) is 23000.In addition, acid number is 15.
The two key equivalents of above-mentioned polymerizable polymer (XX-2) are 1590.
(embodiment 23) polymerizable polymers (XX-3) (monomer ratio, I-a1: II-a1: ARONIX M-5300=30: 57: 13) synthetic
(polymerizable polymer (W-3) 10.0g) heats while stirring with synthetic polymerizable polymer among the 40.1g embodiment 20, under 60 ℃ liquid temperature, drop into 1.0g (0.0070mol, MW:142) glycidyl methacrylate (GMA), 0.006g stopper hydroquinone monomethyl ether and 0.014g (0.000107mol) esterifying catalyst dimethyl benzyl amine, continuing heating then, is 95～105 ℃ scope internal reaction in temperature of reaction.The acid number reactivity reaches 70% when above, and reacting liquid temperature is cooled to below 30 ℃, finishes reaction.Then, drop into the 3.3g pimelinketone, obtain 44.4g polymerizable polymer composition (comprising 10.7g polymerizable polymer (XX-3)) while stir.The weight-average molecular weight of the polymerizable polymer of gained (MW) is 23000.In addition, acid number is 10.Two key equivalents of above-mentioned polymerizable polymer (X-3) (every 1mol ethene unsaturated group corresponding polymers weight) are 2180.
Synthesizing of (comparative example 6) polymerizable polymer (XX-4)
(polymerizable polymer (W-4) 10.0g) heats while stirring with synthetic polymerizable polymer in the 40.1g comparative example 4, under 60 ℃ liquid temperature, drop into 0.77g (0.005mol, MW:142) glycidyl methacrylate (GMA), 0.006g stopper hydroquinone monomethyl ether and 0.015g (0.000114mol) esterifying catalyst dimethyl benzyl amine, continuing heating then, is 95～105 ℃ scope internal reaction in temperature of reaction.The acid number reactivity reaches 90.0% when above, and reacting liquid temperature is cooled to below 30 ℃, finishes reaction.Then, drop into the 2.6g pimelinketone, obtain 43.4g polymerizable polymer composition (comprising 10.7g polymerizable polymer (X-4)) while stir.The weight-average molecular weight of the polymerizable polymer of gained (MW) is 23000.In addition, acid number is 8.Two key equivalents of above-mentioned polymerizable polymer (X-1) (every 1mol ethene unsaturated group corresponding polymers weight) are 2380.
Synthesizing of (comparative example 7) polymerizable polymer (XX-5)
(polymerizable polymer (W-5) 10.0g) heats while stirring with synthetic polymerizable polymer in the 40.1g comparative example 5, under 60 ℃ liquid temperature, drop into 1.60g (0.008mol, MW:200) the acrylate-based glycidyl ether of 4-hydroxybutyl (4HBAGE), 0.0055g stopper hydroquinone monomethyl ether and 0.02g (0.00015mol) esterifying catalyst dimethyl benzyl amine, continuing heating then, is 95～105 ℃ scope internal reaction in temperature of reaction.The acid number reactivity reaches 90.0% when above, and reacting liquid temperature is cooled to below 30 ℃, finishes reaction.Then, drop into the 3.4g pimelinketone, obtain 45.1g polymerizable polymer composition (comprising 11.4g polymerizable polymer (XX-5)) while stir.The weight-average molecular weight of the polymerizable polymer of gained (MW) is 23000.In addition, acid number is 32.
Two key equivalents of above-mentioned polymerizable polymer (XX-5) (every 1mol ethene unsaturated group corresponding polymers weight) are 1580.
7. the manufacturing of multi-functional liquid-crystalline polymer composition-2
The manufacturing-2 of (embodiment 24) multi-functional liquid-crystalline polymer compositions (ZZ-1)
The polymerizable polymer composition (comprising 11.4g polymerizable polymer (XX-1)), 17.1g that input is had a 46.0g embodiment 21 with following formula (VI-a):
The multi-functional liquid crystal liquid crystal property monomer (weight with respect to polymerizable polymer (XX-1) is 1.5 times), 1.4g Photoepolymerizationinitiater initiater IRGACURE 907 of expression is (with respect to polymerizable polymer (XX-1) and formula (gross weight of the multi-functional liquid crystal liquid crystal property monomer of VI-a) is 5%), 97.2g pimelinketone, 0.03g BYK-323 (tensio-active agent) (with respect to the solution stirring mixing of polymerizable polymer (XX-1) and formula (gross weight of the multi-functional liquid crystal liquid crystal property monomer of VI-a) is 0.1%) 1 hour, the multi-functional liquid-crystalline polymer composition of acquisition 160.3g; (in the VI-a), n is 6 to formula.About the contained solids component of composition of the multi-functional liquid-crystalline polymer (Z-1) of gained, two key equivalents are 545, and acid number is 27mgKOH/g.
Synthesizing of (embodiment 25) multi-functional liquid-crystalline polymer compositions (ZZ-2)
Except the polymerizable polymer composition (comprising 10.7g polymerizable polymer (XX-3)) that the polymerizable polymer composition is changed into 44.4g embodiment 23, (the multi-functional liquid crystal liquid crystal property monomer of VI-a) changes 16.1g (weight with respect to polymerizable polymer (XX-3) is 1.5 times) in addition, similarly to Example 24 implementation and operation with formula.About the contained solids component of composition of the multi-functional liquid-crystalline polymer (ZZ-2) of gained, two key equivalents are 599, and acid number is 15mgKOH/g.
Synthesizing of (embodiment 26) multi-functional liquid-crystalline polymer compositions (ZZ-3)
Except Photoepolymerizationinitiater initiater being changed into IRGACURE 907 (gross weight with respect to polymerizable polymer and multi-functional liquid crystal liquid crystal property monomer is 3%) and OXE-02 (gross weight with respect to polymerizable polymer and multi-functional liquid crystal liquid crystal property monomer is 2%), implementation and operation similarly to Example 24.About the contained solids component of composition of the multi-functional liquid-crystalline polymer (ZZ-3) of gained, two key equivalents are 545, and acid number is 27mgKOH/g.
Synthesizing of (comparative example 8) multi-functional liquid-crystalline polymer composition (ZZ-5)
Except the polymerizable polymer composition (10.7g polymerizable polymer (XX-4)) that polymerizable polymer is changed into 43.4g comparative example 6, (the multi-functional liquid crystal liquid crystal property monomer of VI-a) changes 16.1g (weight with respect to polymerizable polymer (XX-4) is 1.5 times) in addition, similarly to Example 24 implementation and operation with following formula.About the contained solids component of composition of the multi-functional liquid-crystalline polymer (ZZ-5) of gained, two key equivalents are 603, and acid number is 12mgKOH/g.
Synthesizing of (comparative example 9) multi-functional liquid-crystalline polymer composition (ZZ-6)
Except the polymerizable polymer composition (11.4g polymerizable polymer (XX-5)) that polymerizable polymer is changed into 45.1g comparative example 7, (the multi-functional liquid crystal liquid crystal property monomer of VI-a) changes 17.1g (weight with respect to polymerizable polymer (XX-5) is 1.5 times) in addition, similarly to Example 24 implementation and operation with following formula.About the contained solids component of composition of the multi-functional liquid-crystalline polymer (ZZ-6) of gained, two key equivalents are 574, and acid number is 49mgKOH/g.
The acid number of composition in the polymkeric substance manufacturing of embodiment 24～26 and comparative example 8,9 and ratio, polymkeric substance, two key equivalent gather and are shown in following table 9.
Table 9.
Figure BPA00001277578400331
8. for the performance evaluation-2 of each multi-functional liquid-crystalline polymer composition
For each multi-functional liquid-crystalline polymer composition of embodiment 24～27 and comparative example 8,9,, the delay (Re/d) of direction in the face of the coating of each film, the transparency, unit thickness is estimated by following method according to following step film forming.
＜film 〉
Handle film for (1) 230 ℃:
The multi-functional liquid-crystalline polymer composition of about 2ml is cast in substrate (polyimide, 10 * 10cm 2) on, make film by spin coating after, make its drying (90 ℃/10 minutes) and make the alignment films of thick 2 μ m, be cooled to 30 ℃.
Then, irradiation exposure 900mJ/cm 2UV-light, handle with alkaline aqueous solution (0.1% aqueous sodium carbonate), only remove the territory, non-exposed area, made film is carried out pyroprocessing (230 ℃/1 hour) after, be cooled to 30 ℃.
＜the transparency 〉
For the film of as above making by visual inspection, based on the following standard evaluation transparency and record.
Zero: transparent
*: albefaction
＜development 〉
Measure in the above-mentioned film when handling and only remove the required time of territory, non-exposed area with alkaline aqueous solution (0.1% aqueous sodium carbonate).
The evaluation of＜optical characteristics 〉
For the film that as above obtains, measure by polarization analysis apparatus OPTIPRO (Xintai City Co., Ltd. of section system) with following condition, try to achieve Re/d.
Measure wavelength X: 550[nm]
The thickness d of film: 2[μ m]
＜orientation uniformity 〉
For the above film that obtains, estimated orientation uniformity with polarization microscope.The film of making is observed under the cross Nicols condition, is not found that the note of the light leak that the orientation defective of liquid crystal produces does zero, not so note do *.
＜stable on heating evaluation 〉
Above-mentioned film further after 3 hours, is tried to achieve Re/d 230 ℃ of heating once more, obtain and the variation of heating preceding Re/d.
＜evaluation result 〉
The result of above-mentioned evaluation gathers and is shown in following table 10.It is as shown in the table, though as can be known the multi-functional liquid-crystalline polymer composition of embodiment 24～26 can provide have good birefringent characteristic, the film transparency and expose the film that birefringent characteristic at high temperature also can not change.
Table 10.
Figure BPA00001277578400351
The possibility of utilizing on the industry
Use the film of composition of the present invention to have following favourable characteristics: to have good birefringence characteristic, even and be exposed to that the birefringence characteristic can not change yet under the high temperature used when making liquid crystal panel. So, if adopt composition of the present invention then polymerizable liquid crystal film that not only can the optics characteristic is good is located at the outside of liquid crystal box, it can also be located in the liquid crystal box, be conducive to realize slimming, the cost degradation of liquid crystal panel. In addition, because not only at room temperature, at high temperature also can keep the optics anisotropy, so also can be used as various electronic devices and holographic material except liquid crystal panel stablely.

Claims (17)

1. polymerizable polymer, it is characterized in that, carry out addition reaction in containing of the hydroxyl of the described polymkeric substance (AP) that contains aromatic nucleus and/or carboxyl and described cyclic monomer between epoxy skeleton or the trimethylene oxide skeleton by the cyclic monomer that contains epoxy skeleton or trimethylene oxide skeleton that makes the polymkeric substance (AP) that contains aromatic nucleus and have a side chain (Q) that contains the ethene unsaturated link(age) and form, the described polymkeric substance (AP) that contains aromatic nucleus comprises with formula I by making:
Figure FPA00001277578300011
The expression (methyl) Acrylic Acid Monomer polymerizable monomer (PM) polymerization and form; In the formula, R 1Be hydrogen atom or methyl, A 1And A 2Independent respectively is the alkylidene group or the singly-bound of carbon number 1～4, B 1Be hydroxyl or carboxyl, X 1For
(i) alkylidene group of carbon number 1～18,
(ii) the phenoxy group side end of adjacency have the carbon number 1～18 of carbonyl alkylidene group,
(iii) the end of the opposition side of described phenoxy group side have Jie with the alkylidene group of the carbon number 1～18 of the alkylidene group of-COO-base bonded carbon number 1～6 or
(iv) the end at the opposition side of described phenoxy group side has 1～10-C of continuous bonded 2H 4The alkylidene group of the carbon number 1～18 of O-base,
A and b are 0 or positive integer and satisfy a+b=0～2.
2. polymerizable polymer as claimed in claim 1 is characterized in that, described polymerizable monomer (PM) also comprises with formula II:
Figure FPA00001277578300012
(methyl) Acrylic Acid Monomer of expression; In the formula, R 2Be hydrogen atom or methyl, A 3And A 4Respectively independent be carbon number 1～4 alkylidene group ,-COO-base or singly-bound, Z 1～Z 3Independent respectively is the alkyl of hydrogen atom, halogen atom, cyano group, carbon number 1～18 or the alkoxyl group of carbon number 1～4, X 2Be the alkylidene group of carbon number 1～18, c and d are 0 or positive integer and satisfy c+d=0～2.
3. as the polymerizable polymer of claim 1 or 2, it is characterized in that described cyclic monomer is with formula III:
The aliphatic monomer that contains epoxy group(ing) of expression, with formula IV:
The aliphatic monomer of the oxygen heterocyclic ring butane group of expression or with formula (V):
Figure FPA00001277578300023
The ester ring type monomer that contains epoxy group(ing) of expression; In the formula, R 3Be the alkyl of hydrogen atom or carbon number 1～4, R 4～R 6Be the alkyl of hydrogen atom or carbon number 1～4, R 7～R 15Alkyl for hydrogen atom or carbon number 1～4.
4. as each the polymerizable polymer in the claim 1～3, it is characterized in that the reactivity of the described polymkeric substance (AP) that contains aromatic nucleus and described cyclic monomer is at 5 moles more than the %.
5. a multi-functional liquid-crystalline polymer composition is characterized in that, comprise in the claim 1～4 each polymerizable polymer and 1 molecule in have the multi-functional monomer of the ethene unsaturated link(age) more than 2.
6. multi-functional polymerizable polymer composition as claimed in claim 5 is characterized in that, multi-functional monomer is with formula VI:
Figure FPA00001277578300024
The multi-functional liquid crystal liquid crystal property monomer of expression; In the formula, R 16Be hydrogen atom or methyl, R 17Have for the alkylidene group of carbon number 1～18 or at the end of the opposition side of (methyl) acryloxy side of adjacency-the COO-base and-alkylidene group of the carbon number 1～18 of either party in the OCO-base, T 1For
Figure FPA00001277578300031
Z 4Be the alkyl of hydrogen atom, halogen atom, carbon number 1～18, Y 1For singly-bound or-COO-, Y 1' be singly-bound or-OCO-.
7. a liquid crystal panel polymer composition is characterized in that, comprises the multi-functional liquid-crystalline polymer composition of claim 5 or 6.
8. a polymerizability film is characterized in that, the multi-functional liquid-crystalline polymer composition of claim 5 or 6 is coated substrate surface form.
9. an optical anisotropic film is characterized in that, the multi-functional liquid-crystalline polymer composition of claim 5 or 6 is coated substrate surface and its curing is formed.
10. polymerizable polymer as claimed in claim 1 is characterized in that, described polymerizable monomer (PM) also comprises with formula II:
(methyl) Acrylic Acid Monomer of expression,
With CH 2=CR 1-X 3The carboxylic monomer of-COOH (formula (C1)) expression and/or with CH 2=CR 1-X 4The carboxylic monomer of-COOH (formula (C2)) expression,
Described carboxylic monomeric total amount is below 15 weight % of the total amount of polymerizable monomer of representing with formula I (PM) and the polymerizable monomer represented with formula II;
In the formula II, R 2Be hydrogen atom or methyl, A 3And A 4Respectively independent be carbon number 1～4 alkylidene group ,-COO-base or singly-bound, Z 1～Z 3Independent respectively is the alkyl of hydrogen atom, halogen atom, cyano group, carbon number 1～18 or the alkoxyl group of carbon number 1～4, X 2Be the alkylidene group of carbon number 1～18, c and d are 0 or positive integer and satisfy c+d=0～2; In the formula (C1), R 1Be hydrogen or methyl, X 3For singly-bound or-COOR 2-, R 2Alkylidene group for carbon number 2～10; In the formula (C2), R 1Be hydrogen or methyl, X 4For-COOR 2OCOR 3-, R 2Be the alkylidene group of carbon number 2～10, R 3The aromatic alkylidene group that contains for the alkylidene group of carbon number 2～10 or carbon number 2～10.
11. the polymerizable polymer as claim 10 is characterized in that, described cyclic monomer is with formula III:
Figure FPA00001277578300041
The aliphatic monomer that contains epoxy group(ing) of expression, with formula IV:
Figure FPA00001277578300042
The aliphatic monomer of the oxygen heterocyclic ring butane group of expression or with formula (V):
Figure FPA00001277578300043
The ester ring type monomer that contains epoxy group(ing) of expression; In the formula, R 3Be the alkyl of hydrogen atom or carbon number 1～4, R 4～R 6Be the alkyl of hydrogen atom or carbon number 1～4, R 7～R 15Alkyl for hydrogen atom or carbon number 1～4.
12. the polymerizable polymer as claim 10 or 11 is characterized in that, the reactivity of the described polymkeric substance (AP) that contains aromatic nucleus and described cyclic monomer is at 5 moles more than the %.
13. a multi-functional liquid-crystalline polymer composition is characterized in that, comprise in the claim 10～12 each polymerizable polymer and 1 molecule in have the multi-functional monomer of the ethene unsaturated link(age) more than 2.
14. the multi-functional polymerizable polymer composition as claim 13 is characterized in that, multi-functional monomer is with formula VI:
Figure FPA00001277578300044
The multi-functional liquid crystal liquid crystal property monomer of expression; In the formula, R 16Be hydrogen atom or methyl, R 17Have for the alkylidene group of carbon number 1～18 or at the end of the opposition side of (methyl) acryloxy side of adjacency-the COO-base and-alkylidene group of the carbon number 1～18 of either party in the OCO-base, T 1For
Figure FPA00001277578300045
Z 4Be the alkyl of hydrogen atom, halogen atom, carbon number 1～18, Y 1For singly-bound or-COO-, Y 1' be singly-bound or-OCO-.
15. a liquid crystal panel polymer composition is characterized in that, comprises the multi-functional liquid-crystalline polymer composition of claim 13 or 14.
16. a polymerizability film is characterized in that, the multi-functional liquid-crystalline polymer composition of claim 13 or 14 is coated substrate surface form.
17. an optical anisotropic film is characterized in that, the multi-functional liquid-crystalline polymer composition of claim 13 or 14 is coated substrate surface and its curing is formed.
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